ENCH 421 – Dr.

Hector De la Hoz Siegler

How to generate a rate expression from a reaction mechanism

1. Is there a rate determining step?

a. If YES, follow a steps

b. If NO, follow b steps

2. Write overall rate expression

a. Set the overall rate expression equal to the rate expression for the rate determining step
divided by its stoichiometric number, assuming it to be irreversible
b. Pick a reactant or product of the overall reaction and set the rate expression for the overall
rate of generation of that species equal to the sum of its rates of generation in each of the
mechanistic steps

3. Simplify overall rate expression by neglecting irreversible or kinetically insignificant steps

4. Decide whether the resulting rate expression is acceptable

It usually won’t be because it will contain concentrations or partial pressures of reactive

intermediates. If it is acceptable, you are done, if not, proceed to step 5

5. Simplify – round 1

a. Write an equilibrium expression for every step except the rate determining step
b. Apply the pseudo-steady state approximation to every reactive intermediate

6. Simplify – round 2

If the mechanism involves a homogeneous catalyst or an enzyme, eliminate one of the

equations from step 5 and replace it with the equation for conservation of catalyst

If the mechanism involves a heterogeneous catalyst, eliminate one of the equations from step 5
and replace it with the equation for conservation of catalytic sites

7. Simplify – round 3

If the mechanism involves charged species, eliminate one of the equations from step 5 and
replace it with the equation for conservation of charge

8. Solve the resulting set of equations

The goal is to get expressions for each of the reactive intermediates in terms of constants (k’s
and Keq’s), concentrations of stable species, and (if appropriate) the initial total amount of
catalyst or enzyme

9. Substitute the concentrations of reactive intermediates into the rate expression (step 4)

1
ENCH 421 – Dr. Hector De la Hoz Siegler

Finding the rate determining step

Important: Not all mechanisms have a rate determining step!

If the Energy vs Reaction Coordinate for a given reaction is known, then it might be possible to
identify a rate determining step by following the procedure outlined below:

1. Divide the reaction sequence into sections:

 The first section begins with the reactants and terminates with the first intermediate that is more
stable than the reactants (i.e. lower energy). This is intermediate I1
 The second section begins with intermediate (I1) and terminates with the next intermediate (I2)
that is more stable than I1.
 Continue this division until you find the products, which concludes the last section.
2. Compute the energy difference between the transition state of highest energy and the initial
intermediate (or reactant) for each section.
 The section with the largest energy difference will contain the rate determining step.
 The rate determining step is the step leading to the transition state of highest energy within the
section identified above.

Example:

Reactants

Products

Reaction coordinate